Tolentino earned Bachelor of Arts in Philosophy in 1980 from the Ateneo de Manila University and his Bachelor of Laws in 1984 from the Ateneo de Manila University Law School.[2]

He later earned a Master of Laws from the University of London, choosing to specialize in Public International Law.[2]

He also earned a Master of National Security Administration (MNSA) from the National Defense College of the Philippines and a Graduate Diploma in Public Administration from the Robert F. Wagner Graduate School of Public Service, New York University[2]

Under his mayoral administration, he created the Tagaytay Office of Public Safety, which later became the basis of policies he put into force as chair of the MMDA. He also initialized the Character First programs which encourages governments, government leaders, civic organizations and religious organizations to band together to establish a "city" or "community" of character with a character traits of a Filipino every month.

Tolentino figured in a minor diplomatic incident on April 5, 2013,[3] when Wang Ben, First Secretary of the Embassy of the People's Republic of China, bumped the rear of the car in front of him along Roxas Boulevard, not knowing that MMDA Chair Tolentino was riding the said car. A chase ensued, with Tolentino and a number of MMDA officials pursuing Wang Ben's vehicle. Media reports say that when finally apprehended, the diplomat's reason for hitting Tolentino's car was "because of irritation caused by the slow-moving traffic."[3] In a letter to Tolentino on April 9, 2013 Chinese Ambassador to the Philippines Ma Keqing formally apologized to Tolentino for the incident.[4]

Tolentino made headlines in May 2013 when he wrote an open letter to author Dan Brown complaining about Brown's description of Manila in his book Inferno as "the gates of hell".[5]

Last August 2013, Tolentino, as the MMDA Chairman, launched the first Metro Manila Integrated Bus Terminal known as the Southwest Integrated Provincial Transport Terminal (SWIPTT). [6]

On September 19, 2013,[7] Tolentino signed Metro Manila Outdoor Media Magna Carta along with various advertising groups, setting the terms for regulating outdoor advertisements in Metro Manila. Among the terms in the 15-page agreement were a 216 square meter limitation on all outdoor signs and structures, with 30 percent of the space of ground level ads allotted "for landscape works or vertical gardens."[7] Prior to the signing of the document, no limit had been placed on the size of advertisements, such that a number of billboards as big as 1,000 square meters had been allowed.[7] The document provided a nine month grace period for advertisers to be able to comply.[7]

As chair of the MMDA, Tolentino is also designated by Metro Manila Commission Executive Order No. 86-09 as chair of the annual Metro Manila Film Festival,[10] in which capacity Tolentino introduced a number of innovations, including the introduction of new contest categories[11] and the removal of box office receipts from the criteria for the selection of best picture.[12]